EP3065856B1 - Gaseous fuel cpox reformers and methods of cpox reforming - Google Patents

Gaseous fuel cpox reformers and methods of cpox reforming Download PDF

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Publication number
EP3065856B1
EP3065856B1 EP14803010.9A EP14803010A EP3065856B1 EP 3065856 B1 EP3065856 B1 EP 3065856B1 EP 14803010 A EP14803010 A EP 14803010A EP 3065856 B1 EP3065856 B1 EP 3065856B1
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Prior art keywords
cpox
gaseous
fuel
reformer
reaction mixture
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German (de)
English (en)
French (fr)
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EP3065856A2 (en
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Caine M. FINNERTY
Paul DEWALD
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Watt Fuel Cell Corp
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Watt Fuel Cell Corp
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    • B01J12/007—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
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    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
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    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
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Definitions

  • the present teachings relate to gaseous fuel catalytic partial oxidation reformers and methods of catalytic partial oxidation reforming of gaseous reformable fuels to produce hydrogen-rich reformates.
  • synthesis gas a product commonly referred to as "synthesis gas” or “syngas”
  • synthesis gas a product commonly referred to as "synthesis gas” or “syngas”
  • fuel reforming operations such as steam reforming, dry reforming, autothermal reforming, and catalytic partial oxidation (CPOX) reforming.
  • CPOX catalytic partial oxidation
  • fuel cells i.e., devices for the electrochemical conversion of electrochemically oxidizable fuels such hydrogen, mixtures of hydrogen and carbon monoxide, and the like, to electricity, to play a greatly expanded role for general applications including main power units (MPUs) and auxiliary power units (APUs).
  • Fuel cells also can be used for specialized applications, for example, as on-board electrical generating devices for electric vehicles, backup power sources for residential-use devices, main power sources for leisure-use, outdoor and other power-consuming devices in out-of-grid locations, and lighter weight, higher power density, ambient temperature-independent replacements for portable battery packs.
  • CPOX reforming or simply CPOX
  • the reaction is exothermic in contrast to steam reforming and dry reforming which are endothermic reactions that require an external source of heat.
  • CPOX reactions are generally faster than other reforming reactions which allows for the construction of relatively small reformers capable of fast start-up and rapid response to changes in load.
  • CPOX reformers also tend to be simpler in design than reformers that require the handling of water and steam, for example, steam reformers and autothermal reformers, which require storage units for water, heating units for the production of steam, burner or combustion units for supplying heat to drive endothermic reforming reactions, and the like, and their associated fluid routing and operation-monitoring and control devices.
  • US 2005/188615 discloses an integrated fuel processor subsystem with quasi-autothermal reforming.
  • the fuel processor disclosed therein includes a catalytic combustor and a quasi-autothermal reformer (QATR).
  • a catalyst bed of catalytic combustor converts an enriched gas stream into a heated H2-containing stream that is used to heat the exterior of tubes 30 of QATR 5 (See, FIGURE 8 (single tube configuration), paragraph [0029], and FIGURES 1 , 3 and 6).
  • Each tube 30 of QATR 5 includes an outer tube 35 and an inner tube 37.
  • Catalyst 36 is located between tube 35 and tube 37 (see paragraph [0036]), not within the gas permeable wall of the reactor tube.
  • each tube 30 of QATR 5 includes outer tube 35 and inner tube 37 that make up the walls W of tube 30 (see FIGURE 9B).
  • Air-fuel-steam (AFS) mixture enters QATR 5 through inlets 32 (see FIGURE 11). The AFS mixture enters into the defined space between outer tube 35 and inner tube 37 that contains catalyst 36.
  • WO 98/41394A discloses a tubular membrane reactor used in a hydrocarbon partial oxidation process. Air is supplied at uniform pressure at the outer surface of the tube and methane and the product syngas flow axially inside the tube. The catalyst layer on the interior surface of the tube.
  • US 2003218991A reports an apparatus for separating oxygen from an oxygen-containing gas and facilitating a chemical reaction with the separated oxygen includes a mixed conducting membrane, a porous body, and a material for catalyzing the reaction.
  • the mixed conducting membrane has respective oxidation and reduction surfaces and is made of a non-porous, gas-impermeable, solid material capable of simultaneously conducting oxygen ions and electrons.
  • WO2008031024 (A1 ) are a reformer having an inner wall containing a solid state membrane, wherein the membrane comprises at least one oxygen anion-conducting oxide selected from the group consisting of hexaaluminates, cerates, perovskites, and other mixed metal oxides that are able to adsorb and dissociate molecular oxygen and a process of reforming a hydrocarbon feed, such as a high sulfur-containing diesel fuel, to produce synthesis gas, suitable for use in fuel cells.
  • a hydrocarbon feed such as a high sulfur-containing diesel fuel
  • EP1 787 950 A2 discloses a fuel reformer comprising: a mixing zone capable of mixing a fuel and an oxidant to form a fuel mixture and a reforming zone disposed downstream of the mixing zone.
  • the reforming zone comprises a primary substrate and a secondary substrate.
  • the primary substrate is disposed upstream of the secondary substrate and has a primary thermal mass that is greater than a secondary thermal mass of the secondary substrate.
  • an igniter may be used to generate combustion gases that heat catalytic material to initiate an exothermic reaction which in turn generates heat theadjacent catalytic material.
  • CPOX reformer includes a catalyst support component, commonly referred to as a “catalyst monolith,” “monolith catalyst support,” “monolith substrate,” or simply a “monolith,” which has a CPOX catalyst or catalyst system deposited thereon.
  • a catalyst support component commonly referred to as a "catalyst monolith,” “monolith catalyst support,” “monolith substrate,” or simply a “monolith,” which has a CPOX catalyst or catalyst system deposited thereon.
  • Monoliths can be classified on the basis of two general configurations: a first configuration characterized by a metal or ceramic body of honeycomb-like, channeled, metallic gauze or spiral-wound corrugated sheet structure presenting an essentially linear gaseous flow path therethrough, and a second configuration characterized by a metal or ceramic foam body of reticulated, or open, pore structure presenting a tortuous gaseous flow path therethrough.
  • first configuration characterized by a metal or ceramic body of honeycomb-like, channeled, metallic gauze or spiral-wound corrugated sheet structure presenting an essentially linear gaseous flow path therethrough
  • a second configuration characterized by a metal or ceramic foam body of reticulated, or open, pore structure presenting a tortuous gaseous flow path therethrough.
  • Representative monoliths of one or the other general type are disclosed in, for example, U.S. Patent Nos.
  • monolith 100 which is of a common prior art type, viewed in longitudinal cross section includes a honeycomb-like ceramic body 101 made up of numerous channels 102 impregnated or wash-coated with CPOX catalyst, an inlet end 103 for admitting a gaseous CPOX reaction mixture, i.e., a mixture of a gaseous oxidizing agent, typically air, and reformable fuel, e.g., a gaseous fuel such as methane, natural gas, propane or butane or a vaporized gaseous fuel such as gasoline, kerosene, jet fuel or diesel, an outlet end 104 for the discharge of hydrogen-rich, carbon monoxide-containing reformate product (syngas) and a CPOX reaction zone 105 which is essentially coextensive with the entire monolith.
  • a gaseous CPOX reaction mixture i.e., a mixture of a gaseous oxidizing agent, typically air
  • reformable fuel e.g., a gaseous fuel
  • CPOX reaction zone 105 can be considered as having an inner, or central, region 106 through which a corresponding inner, or central, portion of a gaseous CPOX reaction mixture stream inherently flows within a relatively high range of velocity V 1 surrounded by an outer, or peripheral, region 107 through which a corresponding outer, or peripheral, portion of the gaseous CPOX reaction mixture stream inherently flows within a relatively low range of velocity V 2 .
  • Monoliths typically experience fairly high CPOX reaction temperatures, for example, on the order of from 600 °C to 1,100 °C. In the case of honeycomb-like monolith 100, these high temperatures, coupled with the inherent differential in flow velocities V 1 and V 2 of the CPOX reaction mixture stream flowing within inner and outer regions 106 and 107, respectively, of CPOX reaction zone 105 tend to account for the observed operational drawbacks of monolith 100 and other essentially linear flow path monoliths where CPOX reforming is concerned.
  • Flashing of the CPOX reaction mixture within radiant heat zone 108 causes undesirable thermal events, raising the temperature to a point where catalyst can be vaporized or deactivated and/or reformer structure can be damaged or rendered inoperative. These thermal events can also lead to cracking of fuel within this zone and, consequently, increased coke (carbon particle) formation resulting in deterioration of CPOX catalyst performance.
  • coke and unreformed higher hydrocarbon fragments contained therein will also deposit upon the anode surfaces of the fuel cells resulting in reduced conversion of product reformate to electricity.
  • the aforementioned differential in flow velocities V 1 and V 2 of the CPOX reaction mixture stream within, respectively, inner and outer regions 106 and 107 of CPOX reaction zone 105 are also primarily responsible for the differential in CPOX reaction temperature ranges T 1 and T 2 in these regions.
  • the higher velocity V 1 of the CPOX reaction mixture stream within inner region 106 results in a higher rate of CPOX reaction therein and an accompanying higher reaction temperature T 1
  • the lower velocity V 2 of the CPOX reaction mixture stream within outer region 107 results in a lower rate of CPOX reaction therein and an accompanying lower reaction temperature T 2 .
  • the temperature profile across inner and outer regions 106 and 107 can be represented by temperature curve 110.
  • a sharp rise in CPOX reaction temperature T 1 if high enough, can result in damage to, and even total destruction of, monolith 100.
  • prior art-type foam monolith 150 viewed in longitudinal cross section includes a ceramic foam body 151 characterized by a reticulated, or open, network of interconnected pores and pore channels 152 supporting a CPOX catalyst or catalyst system deposited thereon by conventional or otherwise known procedures, e.g., impregnation or wash coating.
  • foam monoliths of all types are their higher pressure drops due to their higher resistance to flow compared with linear-flow monoliths such as honeycomb-like monolith 100 of FIG. 1A . Higher pressure drops require higher operational pressures, and therefore higher energy consumption, to meet target flows.
  • Another inherent drawback of foam monoliths lies in the nature of the flow paths of gaseous reactants and reaction products therein (as indicated by the arrows). The characteristic randomness of these flow paths results in very uneven temperature profiles within the monolith (e.g., as indicated by temperature curve 153), increasing the risk of thermal shock due to hot spots and/or reduced CPOX conversion rates due to cold spots.
  • Foam monoliths of all types are also susceptible to flashing much as in the case of the linear flow path monoliths discussed above.
  • foam monoliths are prone to other drawbacks that are characteristic of their kind.
  • they can possess a relatively fragile pore network, especially within their central regions, or they can possess a more robust pore structure throughout. Both types of foam monolith are subject to disadvantages.
  • thermal shock resulting from rapid thermal cycling of the CPOX reformer can over time degrade their structures to the point where the CPOX reaction proceeds in a very inefficient manner, if at all.
  • foam monoliths will differ in their pore structures, and therefore in their gaseous flow properties, from other foam monoliths produced by the same process.
  • individual foam monoliths produced by the same process of manufacture tend to exhibit idiosyncratic operational characteristics that can only be determined empirically.
  • a broader range of performance and reliability parameters or specifications will be assigned to reformers incorporating foam monoliths of the same manufacture in order to make allowance for the unpredictable variations in their performance.
  • the present teachings provide gaseous fuel CPOX reformers and methods of CPOX reforming of gaseous fuels that can address one or more of the deficiencies and/or disadvantages of the state-of-the-art, for example, little or no opportunity or tendency for flashing to occur, no excessively high CPOX reaction temperatures, and/or low back pressures throughout all of its gaseous stream-routing and gaseous flow components and passageways.
  • the present teachings relate to a gaseous fuel CPOX reformer including an array of spaced-apart CPOX reactor units; and an igniter in thermal communication with a CPOX catalyst of at least one CPOX reactor unit of the gaseous fuel CPOX reformer, for example, a CPOX catalyst-containing wall section of at least one CPOX reactor unit.
  • a CPOX reactor unit includes an elongate tube having a wall with an internal surface and an external surface.
  • the wall of the CPOX reactor unit encloses an open gaseous flow passageway and defines an inlet at one end for receiving fluid flow and an outlet at an opposing end for discharge of fluid flow.
  • a CPOX reactor unit is in thermal communication with at least the adjacent CPOX reactor unit(s) in the array.
  • the CPOX reactor unit has at least a section of its wall, including the internal surface, include a CPOX catalyst.
  • the CPOX catalyst-containing wall section is gas-permeable to allow gaseous CPOX reaction mixture to diffuse therein and product hydrogen-rich reformate to diffuse therefrom while remaining structurally stable under CPOX reaction conditions.
  • the gaseous fuel CPOX reformer includes a hydrogen barrier associated with, for example, attached or adhered to, the external surface of at least the CPOX catalyst-containing wall section.
  • the hydrogen barrier also can be associated with a majority, substantially all, or the entire external surface of the wall of a CPOX reactor unit.
  • the hydrogen barrier can be associated with the entire exposed external surface of the wall of a CPOX reactor unit.
  • a pressurized fluid such as a pressurized gas can be a hydrogen barrier, for example, associated with at least the external surfaces of the CPOX catalyst-containing wall section.
  • the CPOX reactor units are generally spaced apart at a distance close enough for the heat from a CPOX reaction in one CPOX reactor unit to initiate a CPOX reaction in one or more adjacent CPOX reactor units.
  • the CPOX reactor units are generally spaced apart at a distance far enough to permit control of the temperature of the CPOX reactor units, particularly at the outlets of the CPOX reactor units. That is, the CPOX reactor units are spaced apart so that heat loss can occur from a CPOX reactor unit to prevent damage to the CPOX reactor unit and if present, to a fuel cell stack that can be in fluid and thermal communication with the outlet(s) of the CPOX reactor unit(s). With such positioning, an array of spaced-apart CPOX reactor units can provide an appropriate thermal balance among the array and can facilitate thermal uniformity throughout or across the array.
  • the gaseous fuel CPOX reformer can include a source of gaseous reformable fuel in fluid communication with the inlets of the CPOX reactor units.
  • the gaseous fuel CPOX reformer can include a single igniter, or can include more than one igniter, for example, two igniters, three igniters or more, where additional igniters can be positioned in thermal communication with CPOX catalyst-containing wall sections of other CPOX reactor units.
  • the CPOX catalyst-containing wall section can include a ceramic or can be a ceramic.
  • the CPOX catalyst containing wall section can be a porous substrate, for example, a porous substrate including a ceramic or a porous ceramic.
  • At least the section of the wall including a CPOX catalyst can be or can include a perovskite.
  • greater than about 20% or greater than about 50% by weight of such wall section can be a perovskite.
  • a CPOX catalyst can be disposed within the wall and/or disposed on an internal surface of the wall.
  • a CPOX catalyst or CPOX catalyst system can be deposited on a wall and/or surface such as the internal surface of a wall, for example, by impregnation, wash coating, or an equivalent procedure.
  • a CPOX catalyst also partially or completely can form the wall, i.e., the structure of the wall.
  • the amount of CPOX catalyst within a catalyst-containing wall section of a CPOX reactor unit can increase along the length of the wall section, for example, in the direction from the inlet end to the outlet end of the CPOX reactor unit, and/or can decrease from the inner surface to the outer surface of the wall.
  • Such gradients of CPOX catalysts, if present, typically are in the CPOX reaction zone of a CPOX reactor unit.
  • the manifold for distributing gaseous CPOX reaction mixture to the inlets of the CPOX reactor units, i.e., the manifold (or the manifold chamber) can be in fluid communication with the inlets of the CPOX reactor units.
  • the manifold includes a manifold housing, where the manifold housing defines a manifold chamber.
  • the manifold can include a gaseous CPOX reaction mixture distributor disposed within, and extending for at least a majority of the length of, the manifold chamber.
  • the gaseous CPOX reaction mixture distributor can be in fluid communication with a conduit that outputs a gaseous CPOX reaction mixture.
  • the gaseous CPOX reaction mixture distributor can include one or more outlets located opposite the inlets of the CPOX reactor units.
  • the manifold can include a heater and/or passive heating elements in thermal communication with the manifold chamber.
  • the manifold can include a cavity, where the manifold housing defines the cavity.
  • a seal can be disposed within or adjacent to the cavity.
  • the manifold housing typically includes a plurality of cavities, wherein the number and arrangement of the cavities coincide with the number and arrangement of the inlets of the CPOX reactor units. The seal can engage the inlet of the CPOX reactor unit thereby providing a gas-tight seal between the manifold housing and the inlet.
  • the present teachings provide a method of gaseous fuel CPOX reforming.
  • Methods of the present teachings generally include introducing a gaseous CPOX reaction mixture including, for example, comprising, consisting essentially of, or consisting of, a gaseous reformable fuel and an oxygen-containing gas into inlets of CPOX reactor units of gaseous fuel CPOX reformers of the present teachings; initiating catalytic partial oxidation of the gaseous CPOX reaction mixture to begin production of a hydrogen-rich reformate; and maintaining catalytic partial oxidation of the gaseous CPOX reaction mixture.
  • introducing a gaseous CPOX reaction mixture includes introducing a gaseous CPOX reaction mixture including a gaseous reformable fuel into inlets of CPOX reactor units, where the CPOX reactor units form an array of spaced-apart CPOX reactor units, each CPOX reactor unit comprising an elongate tube having a wall with an internal surface and an external surface, the wall enclosing an open gaseous flow passageway and defining an inlet and an outlet of the CPOX reactor unit.
  • the CPOX reactor unit can be in thermal communication with at least the adjacent CPOX reactor unit(s) in the array. At least a section of the wall can include a CPOX catalyst.
  • the CPOX catalyst-containing wall section can be gas-permeable to allow gaseous CPOX reaction mixture to diffuse therein and product (hydrogen-rich) reformate to diffuse therefrom.
  • the CPOX catalyst-containing wall section can remain structurally stable under CPOX reaction conditions.
  • the distance between adjacent CPOX reactor units in the array can be as described herein.
  • Initiating catalytic partial oxidation can include initiating a single igniter to begin the CPOX reaction within a CPOX reactor unit, which in turn can initiate the CPOX reaction in the other CPOX reactor units of the gaseous fuel CPOX reformer.
  • initiating catalytic partial oxidation can include initiating a CPOX reaction in one CPOX reactor unit; transferring the heat from the CPOX reaction to an adjacent CPOX reactor unit to initiate a CPOX reaction therein; and repeating transferring the heat to initiate a CPOX reaction in each of the CPOX reactors of the array.
  • Initiating catalytic partial oxidation also can include initiating more than a single igniter, for example, two, three, four, five or more igniters, to begin the CPOX reaction(s) within the CPOX reactor units of the gaseous fuel CPOX reformer.
  • maintaining catalytic partial oxidation of the gaseous CPOX reaction mixture includes transferring heat among the CPOX reactor units within the array thereby to use less external heating than otherwise would be required for the same output of hydrogen-rich reformate.
  • the heat transfer among the array of CPOX reactor units can maintain a predetermined minimum array temperature, for example, about 600 °C or 650 °C.
  • the predetermined minimum array temperature can be substantially uniform across the array of CPOX reactor units.
  • methods of gaseous fuel CPOX reforming can include using the heat of exotherm of the ongoing CPOX reaction and/or heat from some other source to heat the oxygen-containing gas component and/or heat gaseous reformable fuel of the gaseous CPOX reaction mixture about to undergo CPOX reforming.
  • methods of gaseous fuel CPOX reforming can include distributing a gaseous CPOX reaction mixture including a gaseous reformable fuel of substantially uniform composition, at a substantially uniform rate, and/or at a substantially uniform temperature to the inlets of one or more of several CPOX reactor units.
  • methods are provided for CPOX reforming of a gaseous reformable fuel in a start-up mode and in a steady-state mode to produce a hydrogen-rich reformate, where the methods generally can include:
  • the methods described herein can include, for example, in step (i) recited above, adjusting the molar ratio of oxygen to carbon of the gaseous CPOX reaction mixture to correspond to that of a fuel-lean CPOX reaction mixture.
  • the methods can include, for example, in step (iii) recited above, adjusting the molar ratio of oxygen to carbon of the gaseous CPOX reaction mixture to correspond to that of a fuel-rich CPOX reaction mixture.
  • the methods can include flowing fluids such as a gas using a blower or a blower system, for example, a series of blower units.
  • Each blower unit in the series can include a casing having an axial inlet and radial outlet, an impeller disposed within the casing for drawing an oxygen-containing gas at a first pressure in the inlet and expelling oxygen-containing gas at a higher pressure through the outlet, a motor for driving the impeller, and a duct containing the outlet of at least one blower unit in the series in the inlet of at least one other blower unit in the series.
  • at least one blower unit in the series of blower units can provide from 60 % to 90 % of the target gas flow of the blower system.
  • at least one other blower unit in the series of blower units can provide the balance of target gas flow of the blower system.
  • an array of spaced-apart CPOX reactor units can take advantage of the exothermic CPOX reaction to provide a more efficient reforming process.
  • an array of spaced-apart CPOX reactor units of the present teachings can mitigate or eliminate one or more of these drawbacks.
  • the distribution of the total CPOX reforming or CPOX conversion load among an array of spaced-apart CPOX reactor units can simplify and facilitate the maintenance of effective thermal balance and control of the overall CPOX reforming.
  • Such a design can permit more gaseous reformable fuel to be processed for a given CPOX catalyst loading by lowering operating temperatures for a given energy input.
  • the improved thermal management of the gaseous fuel CPOX reformers as described herein also can contribute to the stabilization of the temperature of the CPOX reaction taking place within each of the CPOX reactor units. Consequently, such improved thermal management can maintain suitably uniform CPOX conversion performance among the CPOX reactor units of a gaseous fuel CPOX reformer.
  • the design of the CPOX reformers of the present teachings can take advantage of the exothermic CPOX reaction and can permit an array of spaced-apart CPOX reactor units to be ignited with a minimum number of igniters, for example, a single igniter, whereby the initiation of the CPOX reaction in one of the CPOX reactor units can provide sufficient heat to adjacent CPOX reactor unit(s) to begin the CPOX reforming therein and eventually in each of the CPOX reactor units of the gaseous fuel CPOX reformer.
  • a single igniter can be advantageous in a gaseous fuel CPOX reformer
  • the present teachings contemplate the use of more than a single or one igniter in the gaseous fuel CPOX reformer as the specific size of the array and CPOX reactor units, placement of the CPOX reactor units and igniters, and other factors can contribute to an overall efficient initiation or start-up process for CPOX reforming. Nevertheless, an advantage of distributing the total CPOX conversion load among a plurality of CPOX reactor units in contrast to a single CPOX reactor of comparable fuel conversion capacity is the shorter start-up time.
  • the spaced-apart arrangement of the plurality of CPOX reactor units can simplify the design and manufacture of a related series or line of gaseous fuel CPOX reformers, where individual gaseous fuel CPOX reformers can differ in their fuel-reforming capacities.
  • a new, gaseous fuel CPOX reformer design that desires increased fuel-reforming capacity readily can be constructed by adding additional gaseous fuel CPOX reactor units of standardized specification to an existing design with a few, if any, other significant modifications.
  • compositions are described as having, including, or comprising specific components, or where processes are described as having, including, or comprising specific process steps, it is contemplated that compositions of the present teachings also consist essentially of, or consist of, the recited components, and that the processes of the present teachings also consist essentially of, or consist of, the recited process steps.
  • an element or component is said to be included in and/or selected from a list of recited elements or components, it should be understood that the element or component can be any one of the recited elements or components, or the element or component can be selected from a group consisting of two or more of the recited elements or components.
  • elements and/or features of a composition, an apparatus, or a method described herein can be combined in a variety of ways without departing from the focus and scope of the present teachings, whether explicit or implicit herein. For example, where reference is made to a particular structure, that structure can be used in various embodiments of apparatus of the present teachings and/or in methods of the present teachings.
  • values are disclosed in groups or in ranges. It is specifically intended that the description include each and every individual subcombination of the members of such groups and ranges and any combination of the various endpoints of such groups or ranges.
  • an integer in the range of 0 to 40 specifically is intended to individually disclose 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40
  • an integer in the range of 1 to 20 specifically is intended to individually disclose 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.
  • ceramic in addition to its art-recognized meaning, shall be understood herein to include glasses, glass-ceramics, and cermets (i.e., ceramic-metal composites).
  • gas permeable as it applies to a wall of a CPOX reactor unit herein, shall be understood to mean a wall structure that is permeable to gaseous CPOX reaction mixtures and gaseous product reformate including, without limitation, the gaseous reformable fuel component of the gaseous CPOX reaction mixture and the hydrogen component of the product reformate.
  • liquid reformable fuel shall be understood to include reformable carbon- and hydrogen-containing fuels that are a liquid at standard temperature and pressure (STP) conditions, for example, methanol, ethanol, naphtha, distillate, gasoline, kerosene, jet fuel, diesel, biodiesel, and the like, that when subjected to reforming undergo conversion to hydrogen-rich reformates.
  • STP standard temperature and pressure
  • liquid reformable fuel shall be further understood to include such fuels whether they are in the liquid state or in the gaseous state, i.e., a vapor.
  • gaseous reformable fuel shall be understood to include reformable carbon- and hydrogen-containing fuels that are a gas at STP conditions, for example, methane, ethane, propane, butane, isobutane, ethylene, propylene, butylene, isobutylene, dimethyl ether, their mixtures, such as natural gas and liquefied natural gas (LNG), which are mainly methane, and petroleum gas and liquefied petroleum gas (LPG), which are mainly propane or butane but include all mixtures made up primarily of propane and butane, and the like, that when subjected to reforming undergo conversion to hydrogen-rich reformates.
  • LNG natural gas and liquefied natural gas
  • LPG petroleum gas and liquefied petroleum gas
  • a gaseous reformable fuel also includes ammonia, which like other gaseous reformable fuels, can be stored as a liquid.
  • CPOX reaction shall be understood to include the reaction(s) that occur during catalytic partial oxidation reforming or conversion of a reformable fuel to a hydrogen-rich reformate.
  • gaseous CPOX reaction mixture refers to a mixture including a gaseous reformable fuel and an oxygen-containing gas, for example, air.
  • a gaseous CPOX reaction mixture can comprise, consist essentially of, or consist of, a gaseous reformable fuel and an oxygen-containing gas.
  • the CPOX reaction mixture of the present teachings does not include a liquid reformable fuel, for example, a vaporized liquid reformable fuel or a gaseous liquid reformable fuel.
  • open gaseous flow passageway refers to a conduit or channel for the passage of gas therethrough where a solid, including a porous solid or material, is not present across the entire cross-sectional plane of the conduit or channel, i.e., a conduit or channel free of solids, including porous solids.
  • CPOX catalyst including a porous catalyst such as a monolith cannot be present across the entire internal cross-sectional plane perpendicular to the longitudinal axis of a tubular CPOX reactor unit.
  • Such a structure is distinct from passageways which are packed with a porous catalyst, for example, a monolith, as previously discussed.
  • An open gaseous flow passageway also can be present in a CPOX reactor unit which can be defined as a tube which defines a hollow bore, or a cylindrical substrate defining a hollow bore therethrough along its longitudinal axis.
  • the hollow bore can be considered an open gaseous flow passageway.
  • an open gaseous flow passageway usually can extend along a longitudinal axis of a CPOX reactor unit
  • a tortuous conduit or channel also is contemplated by the present teachings and can be capable of having an open gaseous flow passageway provided that the tortuous conduit or channel is free of solids across a cross-sectional plane of the CPOX reactor unit. It also should be understood that the cross-sectional dimension(s) of an open gaseous flow passageway can vary long its longitudinal axis or along the tortuous conduit or channel.
  • An important feature of a gaseous fuel CPOX reformer of the present teachings is the array of spaced-apart CPOX reactor units.
  • An array of CPOX reactor units can refer to an orderly arrangement or a regular placement of a CPOX reactor unit in relation to the other CPOX reactor unit(s). In other words, the CPOX reactor units typically are not randomly positioned or placed. Although straight line, square, and rectangular configurations are commonly used, other configurations such as hexagonal and octagonal are contemplated by the present teachings.
  • the arrangement or placement of the CPOX reactor units can be determined by various factors including, among others, the positioning and configuration of the plurality of CPOX reactor units, the materials of construction of the CPOX reactor units such as its walls and CPOX catalyst, the gaseous reformable fuel, the operating temperature of the CPOX reactor units, and the desired use and output of product hydrogen-rich reformate, for example, the materials of construction of a hydrogen reformate-consuming device such as a fuel cell unit or system to which the CPOX reformer is to be connected or coupled.
  • the CPOX reactors units will not be thermally connected or have insufficient thermal communication, for example, to initiate a CPOX reaction in an adjacent CPOX reactor unit and/or to maintain a heat transfer zone roughly encompassing the plurality of CPOX reactor units. Conversely, if the distance between or among (adjacent) CPOX reactor units is too small, the CPOX reactor units may be subjected to overheating and degradation, which can result in malfunction of the gaseous fuel CPOX reformer.
  • CPOX reformers of the present teachings is an igniter for initiating the CPOX reaction within the CPOX reactor units, for example, an array of CPOX reactor units.
  • a single igniter can be used to initiate a CPOX reaction within each of the CPOX reactor units of a gaseous fuel CPOX reformer.
  • more than a single or one igniter for example, two igniters, three igniters, or more than three igniters can be used to initiate or start the CPOX reaction within the CPOX reactor units.
  • the number and placement of the igniter(s) can be determined by various parameters including, for example, the design, structure and placement of the CPOX reactor units, and the desired efficiency and rapidity of start-up of a gaseous fuel CPOX reformer.
  • An igniter can include a radiant heat-producing element positioned in proximity to, but in physical isolation from, an internal surface of a CPOX reactor unit, which also can be disposed within a chamber.
  • an igniter can transmit radiant heat to an exposed internal surface and/or CPOX catalyst of at least one CPOX reactor unit in proximity thereto to initiate the CPOX reaction therein.
  • radiant heat produced by the CPOX reaction occurring within the CPOX reaction zone of the at least one CPOX reactor unit in turn can initiate a CPOX reaction within at least one other CPOX reactor unit, typically also within the chamber, until in such manner the CPOX reaction has been initiated in all of the CPOX reactor units of the gaseous fuel CPOX reformer.
  • a hydrogen barrier is associated with, such as attached to, the external surface of at least the catalyst-containing wall section of a tubular CPOX reactor unit, which catalyst-containing wall section typically defines the CPOX reaction zone.
  • the hydrogen barrier can be attached to the entire external surface of the wall of a CPOX reactor unit.
  • the hydrogen barrier can prevent or inhibit the loss of hydrogen from the CPOX reactor unit. In the absence of such a barrier, hydrogen may diffuse through and beyond the catalyst-containing wall section of the CPOX reactor unit rather than exit the CPOX reactor unit through its outlet.
  • a gaseous fuel CPOX reformer can include a source of gaseous reformable fuel.
  • the source of gaseous reformable fuel can include a tank or other container for storage and/or delivery of a gaseous reformable fuel to the gaseous fuel CPOX reformer, for example, to the inlets of CPOX reactor units.
  • a gaseous fuel CPOX reformer can include an array of spaced-apart CPOX reactor units; an igniter in thermal communication with a CPOX catalyst of at least one CPOX reactor unit; and a source of gaseous reformable fuel in fluid communication with inlets of CPOX reactor units.
  • the CPOX reactor units can include an elongate tube, for example, a cylinder, defining a hollow bore, having a gas-permeable ceramic wall with an internal surface and an external surface, where at least a section of the gas-permeable ceramic wall comprises a CPOX catalyst.
  • the gas-permeable ceramic wall can enclose an open gaseous flow passageway and defines an inlet and an outlet of the CPOX reactor unit.
  • a gaseous fuel CPOX reformer can include a plurality of spaced-apart CPOX reactor units, each CPOX reactor unit comprising an elongate tube having an inlet for gaseous CPOX reaction mixture, and an outlet for hydrogen-rich reformate, a wall with internal and external surfaces, the wall enclosing an open gaseous flow passageway with at least a portion of the wall having CPOX catalyst disposed therein, comprising its structure or a combination thereof, such catalyst-containing wall section and open gaseous flow passageway enclosed thereby defining a gaseous phase CPOX reaction zone, the catalyst-containing wall section being gas-permeable to allow gaseous CPOX reaction mixture to diffuse therein and product hydrogen-rich reformate to diffuse therefrom while remaining stable under CPOX reaction conditions.
  • heat recovered from the exotherm of an ongoing CPOX reaction and/or heat recovered from one or more other heat sources can be utilized to heat oxygen-containing gas and/or heat gaseous reformable fuel prior to formation of a gaseous CPOX reaction mixture.
  • an igniter for initiating the CPOX reaction within an array of CPOX reactor units for example, during a start-up mode of operation of a gaseous fuel CPOX reformer, is in thermal communication with a CPOX catalyst, for example, in a CPOX reaction zone.
  • the igniter can initiate a CPOX reaction in at least one CPOX reactor unit proximate thereto with heat of exotherm within the at least one CPOX reactor unit in turn initiating the CPOX reaction within one or more other CPOX reactor units within the array.
  • a manifold or plenum in fluid communication with the inlets of CPOX reactor units, can be configured to provide a more uniform distribution of gaseous CPOX reaction mixture, for example, at a substantially uniform composition, at a substantially uniform temperature and/or at a substantially uniform rate, to inlets of CPOX reactor units.
  • a manifold can have a housing or enclosure defining a manifold chamber.
  • a manifold or manifold chamber can include a gas distributor, for example, a gas distributor within the manifold chamber.
  • the gas distributor can be considered a gaseous fuel CPOX reaction mixture distributor.
  • the housing or enclosure can be fabricated from a relatively low cost, readily moldable thermoplastic or thermosetting resin and/or can feature "cold seal" connections between its outlets and the inlets of the CPOX reactor units.
  • a manifold can be in fluid communication with the inlet of at least one CPOX reactor unit, where the manifold includes a manifold housing.
  • the manifold housing can define a manifold chamber.
  • the manifold can include one or more additional components such as a gaseous CPOX reaction mixture distributor, a heater, and a cavity including a seal.
  • the gaseous CPOX reaction mixture distributor can be disposed within, and extending for at least a majority of the length of, the manifold chamber, where is in fluid communication with a gaseous reactants conduit, and the gaseous CPOX reaction mixture distributor includes one or more outlets located opposite the inlet of the CPOX reactor unit.
  • a gaseous CPOX reaction mixture distributor can include a housing defining a chamber, for example, a closed-ended hollow tube or other structure, typically having a length greater than its width and depth.
  • the housing can define a one or more outlets providing fluid communication between the interior of the housing or chamber and the exterior of the housing.
  • the one or more outlets can be along one side of the gaseous CPOX reaction mixture distributor or form a line or longitudinal array along its longitudinal axis, for example, in the case of a tubular gaseous CPOX reaction mixture distributor.
  • the one or more outlets of the gaseous CPOX reaction mixture distributor When positioned in the manifold chamber, usually are located opposite the inlets of the CPOX reactor units.
  • the CPOX reaction mixture is initially introduced into the manifold chamber in a direction away from the inlets of the CPOX reactors units, for example, downward towards the bottom of the manifold chamber and then will flow towards the inlets of the CPOX reactor units, for example, flowing upwards to the inlets.
  • a heater can be in thermal communication with the manifold chamber.
  • the heater can be an electrical resistance heater.
  • the heater can be disposed within the manifold chamber.
  • the heater can include a passive heating element such as at least one thermally conductive element in thermal communication with the manifold and a CPOX reaction zone of CPOX reactor unit thereby to transfer heat of exotherm from the CPOX reaction zone and/or CPOX reactor unit to the manifold.
  • the manifold housing can define one or more cavities.
  • a seal can be disposed within or adjacent to the cavity, where the seal can engage the inlet of the CPOX reactor unit and can provide a gas-tight seal between the manifold housing and the inlet.
  • the manifold housing can include the same number of cavities as CPOX reactor units such that each CPOX reactor unit can be in fluid communication with the manifold chamber and each cavity can include a seal securing a respective CPOX reactor unit.
  • the cavities of the manifold housing can be sized and arranged in the same configuration as the inlets of the CPOX reactor units to provide a match for each cavity to an inlet.
  • the seal can be a gasket.
  • the manifold housing can be fabricated from or include a material that remains thermally and mechanically stable at the temperature of operation of the CPOX reactor units.
  • the walls of the CPOX reactor units can include at least two regions, a first, or upstream, region being substantially devoid of CPOX catalyst and enclosing an essentially CPOX reaction-free zone of relatively low operating temperature and a second, or downstream, region containing CPOX catalyst and enclosing a CPOX reaction zone of relatively high operating temperature.
  • a blower system featuring an interconnected series of individual centrifugal blower units can be used to introduce a flow of oxygen-containing gas into the reformer and/or can provide for gas flow within the CPOX reformer, for example, for heat transfer, which can include heating and/or cooling of structure(s) and thermal zone(s).
  • a control system can be adapted to control the operations of the CPOX reformer in its start-up, steady-state, and/or shut-down modes.
  • a gaseous fuel CPOX reformer of the present teachings can include a conduit for routing gas toward the inlets of the CPOX reactor units.
  • the conduit can include an inlet for oxygen-containing gas, an inlet for gaseous reformable fuel, a mixing zone in which oxygen-containing gas and gaseous reformable fuel combine to provide a gaseous CPOX reaction mixture, and/or an outlet for gaseous CPOX reaction mixture.
  • the conduit can be generally U-shaped.
  • a gaseous fuel CPOX reformer of the present teachings can include a mixer, for example, to mix oxygen-containing gas and gaseous reformable fuel.
  • the mixer can be a static mixer or a dynamic mixer, for example, a fluid mixing device such as described in co-pending, co-owned U.S. Patent Application No. 14/335,463 , entitled, "Mixing Reformable Fuels and an Oxygen-Containing Gas and/or Steam,".
  • a gaseous fuel CPOX reformer of the present teachings can include a CPOX reformate processing unit or device, for example, a carbon monoxide removal device to reduce the carbon monoxide content of the product reformate.
  • a CPOX reformate processing unit or device can include a water gas shift converter, a preferential oxidation reactor, and/or a hydrogen-selective membrane for separating reformate into a hydrogen stream and a carbon monoxide-containing stream.
  • a gaseous fuel CPOX reformer of the present teachings can have one or more outlets of CPOX reactor units directly connected to inlet(s) of another device, for example, a fuel cell.
  • outlets of CPOX reactor units can be in fluid communication with a manifold or similar component or device that can combine the effluent stream from multiple CPOX reactor unit outlets and distribute such combined effluent to an equal, a greater, or a lesser number of inlets of another device, for example, an anode of a fuel cell.
  • a gaseous fuel CPOX reformer of the present teachings can include thermal insulation for reducing heat loss from the tubular CPOX reactor units and other heat radiating components of the reformer.
  • a gaseous fuel CPOX reformer of the present teachings can include a gaseous stream driver for driving gaseous flow within and through the CPOX reformer.
  • the gaseous stream driver can be a blower or blower system.
  • a gaseous fuel CPOX reformer of the present teachings can include a fuel pump. Examples of a pump such as a fuel pump include a metering pump, a rotary pump, an impeller pump, a diaphragm pump, a peristaltic pump, a positive displacement pump, a gear pump, a piezoelectric pump, an electrokinetic pump, an electroosmotic pump and a capillary pump.
  • a gaseous fuel CPOX reformer of the present teachings can include one or more sensor assemblies for monitoring and controlling one or more reformer operations. Examples of sensor assemblies include flow meters, thermocouples, thermistors, and resistance temperature detectors.
  • a gaseous fuel CPOX reformer of the present teachings also can include a control system for automating the operations of the reformer in its start-up, steady-state, and/or shut-down modes. The control system can include a plurality of sensor assemblies in communication with a controller.
  • a gaseous fuel CPOX reformer of the present teachings can include heat transfer means in thermal communication with the CPOX reactor units.
  • the heat transfer means can transfer heat from the CPOX reactor units during a steady-state mode of operation of the gaseous fuel CPOX reformer, for example, to maintain the temperature within the CPOX reaction zone of the CPOX reactor units within a preset range.
  • Heat transfer means can include a blower, for example, to direct a coolant stream against exposed exterior surfaces of the CPOX reactor units and/or against a heat-radiative member of a heat conducting assembly in thermal communication with exposed surfaces of CPOX reactor units.
  • a gaseous fuel CPOX reformer of the present teachings also can include a blower for other purposes. For example, a blower can introduce oxygen-containing gas into a conduit and/or drive gaseous flow within a CPOX reactor unit.
  • a blower can include a series of blower units.
  • a blower or blower unit in a series can include a casing having an axial inlet and a radial outlet, an impeller disposed within the casing for drawing in a gas, for example, an oxygen-containing gas such as air, in the axial inlet and expelling the gas through the radial outlet; and a motor for driving the impeller.
  • the blower can draw in a gas at a first pressure and expel the gas at a second, for example, higher, pressure.
  • a blower also can include a duct to contain the outlet of at least one blower unit in the series with the inlet of at least one other blower unit in the series.
  • a series of blowers can include the blower systems as described in co-owned U.S. Patent Application Publication No. 2012/0328969 , entitled, "Centrifugal Blower System and Fuel Cell Incorporating Same,".
  • a gaseous fuel CPOX reformer of the present teachings can include a source of electrical current for powering electrical energy-consuming reformer components and/or auxiliary CPOX reformer components.
  • the source of electrical current can include a rechargeable battery and battery recharger.
  • methods of CPOX reforming are provided. More specifically, the present teachings provide methods of CPOX reforming of a gaseous reformable fuel to a hydrogen-rich reformate or product. To that end, in various embodiments, the methods of CPOX reforming can include:
  • the methods can include heating oxygen-containing gas at ambient temperature or at an ambient temperature prior to its introduction into a conduit using heat from an external heat-producing source. In various embodiments, the methods can include heating further the oxygen-containing gas from a first temperature to a second elevated temperature, for example, using heat of exotherm recovered from the CPOX reaction occurring within the CPOX reaction zones of the CPOX reactor units.
  • the methods can include making the gaseous CPOX mixture more uniform in composition, for example, substantially uniform in composition, prior to its introduction into the inlets of the CPOX reactor units.
  • the methods can include distributing the gaseous CPOX reaction mixture of substantially uniform composition to the inlets of the CPOX reactor units and/or distributing the gaseous CPOX reaction mixture to the inlets of the CPOX reactor units at a substantially uniform temperature.
  • the methods include distributing the gaseous CPOX reaction mixture to the inlets of the CPOX reactor units such that the difference in flow rate of the CPOX reaction mixture within any two CPOX reactor units is not greater than about 20 % and/or the difference in the temperature of CPOX reaction mixture entering the inlets of any two CPOX reactor units in not greater than about 10 %.
  • the methods can include initiating CPOX of the gaseous CPOX reaction mixture within the CPOX reaction zones of the CPOX reactor units by operating an igniter, where radiant heat output from the igniter can be transmitted to an exposed section of at least one CPOX reactor unit in proximity thereto to initiate the CPOX reaction therein, radiant heat produced by the CPOX reaction occurring within the CPOX reaction zone of the at least one CPOX reactor unit in turn initiating the CPOX reaction within at least one other CPOX reactor unit within the chamber until in such manner the CPOX reaction has been initiated in all of the CPOX reactor units in the chamber.
  • the methods can include adjusting the molar ratio of oxygen to carbon of the gaseous CPOX reaction mixture to correspond to that of a fuel-lean CPOX reaction mixture, for example, in step (iii) recited above. In certain embodiments, the methods can include adjusting the molar ratio of oxygen to carbon of the gaseous CPOX reaction mixture to correspond to that of a fuel-rich CPOX reaction mixture, for example, in step (vii) recited above.
  • the methods of the present teachings include providing gas flow by a blower system including a series of blower units, each blower unit in the series comprising a casing having an axial inlet and radial outlet, an impeller disposed within the casing for drawing an oxygen-containing gas at a first pressure in the inlet and expelling oxygen-containing gas at a higher pressure through the outlet and a motor for driving the impeller, and a duct containing the outlet of at least one blower unit in the series in the inlet of at least one other blower unit in the series, at least one blower unit in the series providing from 60 to 90% of the target gas flow of the blower system and the at least one other blower unit in the series providing the balance of the target gas flow of the blower system.
  • the methods can include a back pressure in the CPOX reformer of not more than about 2. 746.5 Pa (three (3) inches of water).
  • FIG. 2 illustrates one embodiment of a gaseous fuel CPOX reformer in accordance with the present teachings.
  • gaseous fuel CPOX reformer 200 includes centrifugal blower 202 for introducing oxygen-containing gas, exemplified here and in the other embodiments of the present teachings by air, into conduit 203 , and for driving this and other gaseous streams (inclusive of gaseous fuel-air mixture(s) and hydrogen-rich reformates) through the various passageways, including open gaseous flow passageways, of the CPOX reformer.
  • Conduit 203 can include flow meter 204 and thermocouple 205 . These and similar devices can be placed at various locations within a gaseous fuel CPOX reformer in order to measure, monitor and control the operation of the gaseous fuel CPOX reformer as more fully explained in connection with the control system illustrated in FIG. 3A .
  • air introduced by blower 202 into conduit 203 combines with gaseous reformable fuel, exemplified here and in the other embodiments of the present teachings by propane, introduced into conduit 203 at a relatively low pressure from gaseous fuel storage tank 213 through fuel line 214 equipped with optional thermocouple 215, flow meter 216, and flow control valve 217.
  • propane introduced into conduit 203 at a relatively low pressure from gaseous fuel storage tank 213 through fuel line 214 equipped with optional thermocouple 215, flow meter 216, and flow control valve 217.
  • propane introduced into conduit 203 at a relatively low pressure from gaseous fuel storage tank 213 through fuel line 214 equipped with optional thermocouple 215, flow meter 216, and flow control valve 217.
  • propane introduced into conduit 203 at a relatively low pressure from gaseous fuel storage tank 213 through fuel line 214 equipped with optional thermocouple 215, flow meter 216, and flow control valve 217.
  • the air and propane combine in mixing zone 218 of conduit 203.
  • a mixer for example, a static mixer such as in-line mixer 219, and/or vortexcreating helical grooves formed within the internal surface of conduit 203, or an externally powered mixer (not shown), are disposed within mixing zone 218 of conduit 203 to provide a more uniform propane-air gaseous CPOX reaction mixture than would otherwise be the case.
  • the propane-air mixture enters manifold, or plenum, 220 which functions to distribute the reaction mixture more evenly into tubular CPOX reactor units 209, a detailed description of one embodiment of which is presented herein in connection with tubular CPOX reactor units 408 of manifold portion 450 illustrated in FIG. 4E .
  • igniter 223 initiates the gaseous phase CPOX reaction of the gaseous CPOX reaction mixture within CPOX reaction zones 210 of tubular CPOX reactor units 209 thereby commencing the production of hydrogen-rich reformate.
  • Thermocouple 225 is positioned proximate to one or more CPOX reaction zones 210 to monitor the temperature of the CPOX reaction occurring within CPOX reactor units 209 , the temperature measurement being relayed as a monitored parameter to reformer control system 226.
  • Reformer 200 can also include a source of electrical current, for example, rechargeable lithium-ion battery system 227, to provide power for its electrically driven components such as blower 202 , flow meters 204 and 216, flow control valve 217, and igniter 223.
  • product effluent for example, hydrogen-rich reformate
  • a gaseous fuel CPOX reformer can be introduced into one or more conventional or otherwise known carbon monoxide removal devices for the reduction of its carbon monoxide (CO) content, for example, where the product effluent is to be introduced as fuel to a fuel cell stack utilizing a catalyst that is particularly susceptible to poisoning by CO, for example, a polymer electrolyte membrane fuel cell.
  • carbon monoxide removal device 228 can be in direct fluid communication with the outlets of CPOX reactor units 209 .
  • the product effluent can be introduced into a water gas shift (WGS) converter wherein CO is converted to carbon dioxide (CO 2 ) while at the same time producing additional hydrogen, or the product effluent can be introduced into a reactor wherein CO is made to undergo preferential oxidation (PROX) to CO 2 .
  • WGS water gas shift
  • PROX preferential oxidation
  • CO reduction can also be carried out employing a combination of these processes, for example, WGS followed by PROX and vice versa.
  • Units/devices of this kind can also be combined with one or more other CO-reduction units such as the aforementioned WGS converter and/or PROX reactor.
  • Control system 300 illustrated in FIG. 3A is provided for controlling the operations of a gaseous fuel CPOX reformer in accordance with the present teachings.
  • control system 300 includes controller 301 to manage gaseous fuel CPOX reformer 302 in its start-up, steady-state, and shut-down modes of operation.
  • the controller can be software operating on a processor. However, it is within the scope of the present teachings to employ a controller that is implemented with one or more digital or analog circuits, or combinations thereof.
  • Control system 300 further includes a plurality of sensor assemblies, for example, thermocouple and associated fuel pressure meter 304 , thermocouple and associated air pressure meter 309 , and reformer thermocouple 314, in communication with controller 301 and adapted to monitor selected operating parameters of CPOX reformer 302 .
  • sensor assemblies for example, thermocouple and associated fuel pressure meter 304 , thermocouple and associated air pressure meter 309 , and reformer thermocouple 314, in communication with controller 301 and adapted to monitor selected operating parameters of CPOX reformer 302 .
  • a controller can manage the operations of a gaseous fuel CPOX reformer. More specifically, a controller can communicate with a control signal-receiving portion of the desired section or component of a gaseous fuel CPOX reformer by sending command signals thereto directing a particular action.
  • controller 301 can send control signals to fuel flow control valve 305 , for example, to control the flow of fuel from gaseous fuel storage tank 303 through fuel line 306 to conduit 307 , to centrifugal blower 308 to control the flow of air into conduit 307 and drive the flow of gaseous CPOX reaction mixture within and through CPOX reformer 302 , to igniter 311 to control its on-off states, and to battery/battery recharger system 312 to manage its functions.
  • the sensor assemblies, control signal-receiving devices and communication pathways herein can be of any suitable construction and of those known in the art.
  • the sensor assemblies can include any suitable sensor devices for the operating parameters being monitored. For example, fuel flow rates can be monitored with any suitable flow meter, pressures can be monitored with any suitable pressure-sensing or pressure-regulating device, and the like.
  • the sensor assemblies can also, but do not necessarily, include a transducer in communication with the controller.
  • the communication pathways will ordinarily be wired electrical signals but any other suitable form of communication pathway can also be employed.
  • communication pathways are schematically illustrated as single- or double-headed arrows.
  • An arrow terminating at controller 301 schematically represents an input signal such as the value of a measured flow rate or measured temperature.
  • An arrow extending from controller 301 schematically represents a control signal sent to direct a responsive action from the component at which the arrow terminates.
  • Dual-headed pathways schematically represent that controller 301 not only sends command signals to corresponding components of CPOX reformer 302 to provide a determined responsive action, but also receives operating inputs from CPOX reformer 302 and mechanical units such as fuel control valve 305 and blower 308 and measurement inputs from sensor assemblies such as pressure meters 304 and 309 and thermocouple 314.
  • FIG. 3B presents a flow chart of an exemplary control routine that can be executed by a controller of a control system to automate the operations of a gaseous fuel CPOX reformer.
  • the flow chart can be executed by a controller at a fixed interval, for example, every 10 milliseconds or so.
  • the control logic illustrated in FIG. 3B performs several functions including the management of gaseous flows and CPOX reaction temperatures in start-up and steady-state modes of operation and management of the procedure for the shut-down mode of reformer operation.
  • FIGS. 4A-4K which are representative of further embodiments of the present teachings
  • air as an oxygen-containing gas is introduced at a preset mass flow rate via centrifugal blower system 402 , shown in greater detail in FIGS. 4J and 4K , through inlet 403 of conduit 404 .
  • Propane is introduced into conduit 404 via fuel line 441 and fuel inlet 442. Propane and air begin to combine in mixing zone 420 of conduit 404 to provide a gaseous CPOX reaction mixture.
  • a mixer of any suitable kind for example, a static mixer disposed within mixing zone 420 and/or a helically-grooved internal wall surface of conduit 404 , can be included to provide a gaseous CPOX reaction mixture of greater compositional uniformity than otherwise would form in mixing zone 420 .
  • gaseous CPOX reaction mixture exits conduit 404 through outlet 425 and enters gas distributor 427 of manifold 426, which is configured to provide a more uniform distribution of the reaction mixture to, and within, tubular CPOX reactor units 408 .
  • gas distributor 427 of manifold 426 is configured to provide a more uniform distribution of the reaction mixture to, and within, tubular CPOX reactor units 408 .
  • Such an arrangement or other arrangement within the present teachings can provide a distribution of gaseous CPOX reaction mixture where the difference in flow rate of the gaseous CPOX reaction mixture within any two CPOX reactor units is not greater than about 20 percent, for example, not greater than about 10 percent, or not greater than about 5 percent.
  • manifold 426 (an enlarged longitudinal cross section view of a portion of which is illustrated in FIG. 4E together with associated tubular CPOX reactor units 408 ) includes manifold housing, or enclosure, 428 defining manifold chamber 429 within which gaseous CPOX reaction mixture (gas) distributor 427 is connected to outlet 425 of conduit 404 .
  • Gaseous CPOX reaction mixture exiting conduit 404 through outlet 425 enters gas distributor 427 thereafter passing outwardly through apertures (e.g., holes or slots) 430 located at the bottom or lower part of the gas distributor, the gas then flowing around the exterior surface of the distributor to its top or upper part and from there into inlets 431 of tubular CPOX reactor units 408 .
  • apertures e.g., holes or slots
  • Some specific factors that can bear upon the optimization of the design of a manifold for accomplishing its function of promoting a more uniform distribution of gaseous CPOX reaction mixture to CPOX reactor units include the configuration of its housing, the volume of its chamber, and the dimensions of the gas distributor including the number, design and placement of its orifices. Such factors in turn depend on such reformer design and operational factors as the target flow rates of gaseous CPOX reaction mixture within a conduit, the number and arrangement of CPOX reactor units, the shape and dimensions of inlets of CPOX reactor units, and similar considerations.
  • a manifold of optimal fuel-air distribution performance for a particular gaseous fuel CPOX reformer in accordance with the present teachings can be readily constructed by those skilled in the art employing routine testing methods.
  • a manifold housing can be fabricated from a material that remains thermally and mechanically stable at the high temperatures that are typical of CPOX reforming.
  • various kinds of refractory materials including refractory composites such as carbon fiber-and/or glass fiber-reinforced ceramics, are suitable for fabricating the manifold housing.
  • Suitable materials of construction include dense ceramics such as various known types of alumina, recrystallized alumina, alumino-silicates, boron nitride, glass-ceramics, magnesium oxide, zirconium phosphate, and the like, metals such as nickel-chromium-based super alloys, Hastelloy super alloys, and the like.
  • dense ceramics such as various known types of alumina, recrystallized alumina, alumino-silicates, boron nitride, glass-ceramics, magnesium oxide, zirconium phosphate, and the like
  • metals such as nickel-chromium-based super alloys, Hastelloy super alloys, and the like.
  • these and other refractory materials tend to be relatively high in cost and can also be challenging to work with, especially in the case of manufacturing articles with relatively complex configurations.
  • gas-permeable wall 451 of CPOX reactor units 408 can be divided along its length into a first, or upstream, region 452, starting at its fuel-air mixture inlet 431, that is substantially devoid of CPOX catalyst, and a second, or downstream, region 453, starting at the end of first region 452 and ending at or proximate to product reformate effluent outlet 454 of the reactor unit, that contains a catalytically effective amount of CPOX catalyst 464.
  • this embodiment of CPOX reactor unit largely confines hot CPOX reaction zones 409 to their second regions 453 leaving its essentially CPOX catalyst-free first region 452 to remain at a considerably lower temperature, for example, in the region of from ambient to up about 350 °C, particularly at the juncture of fuel-air mixture inlets 431 of CPOX reactor units 408 and manifold housing 428.
  • thermoplastic and thermoset resins that can be used for the fabrication of a manifold housing include polyetherimide (PEI), polyaryletherketones (PAEKs) such as polyether ether ketone (PEEK), phenolformaldehyde resins, and the like.
  • thermally stable resins in addition to their relatively low material cost, have the added advantage of being readily formable into complex shapes employing low cost manufacturing procedures such as extrusion molding, vacuum molding, injection molding, reaction injection molding, rotational molding, and the like, and are therefore well suited for making manifold housings having relatively complex geometries.
  • gaseous CPOX reaction mixture enters inlets 431 of CPOX reactor units 408 and into CPOX reaction zones 409 where the reaction mixture undergoes a gaseous phase CPOX reaction to produce a hydrogen-rich, carbon monoxide-containing reformate.
  • one or more igniter(s) 435 initiates CPOX.
  • CPOX becomes self-sustaining, for example, when the temperature of the reaction zone reaches from about 250 °C to about 1100 °C, the igniter(s) can be shut off as external ignition no longer is required to maintain the now self-sustaining CPOX reaction.
  • Thermal insulation 410 for example, of the microporous or alumina-based refractory type, surrounds those portions of the CPOX reformer to reduce thermal losses from these components.
  • FIGS. 4A-4D illustrate an embodiment of the present teachings where two igniters 435 (one for each array) are used to initiate a CPOX reaction within CPOX reaction zones 409 of CPOX reactor units 408 in a chamber during the start-up mode of operation of reformer 400 .
  • CPOX reactor units 408 are arranged in two separate 2x7 arrays with each array being disposed within chamber 436.
  • the perimeter of an array marks the boundary between open space 438 of chamber 436 and thermal insulation 410.
  • Exterior surfaces 437 of the walls of CPOX reactor units 408 corresponding to at least a portion of their CPOX reaction zones 409 are exposed within open space 438.
  • the hydrogen barrier can be the exposed, exterior surface of a CPOX reactor unit.
  • Igniters 435 of the electrical resistance type, for example, rated at from 10 to 80 watts or greater, are disposed at opposite ends of chamber 436 where then radiant heat-producing elements 439 are positioned in proximity to, but in physical isolation from, exterior surfaces 437 of CPOX reactor units 408 .
  • Thermocouples 440 are disposed at the ends of chamber 436 opposite igniters 435 in order to monitor the temperature of CPOX reaction zones 409 and provide a reformer control input as described in connection with the control system illustrated in FIG. 3A .
  • Operation of the igniters causes radiant heat to be transferred to, and through, the walls of one or more nearby CPOX reactor units whereby CPOX is initiated within the CPOX reaction zone of such reactor unit(s).
  • the thermal radiation emitted from the CPOX reaction zone(s) of these nearby CPOX reactor units then can initiate CPOX within the reaction zones of the remaining CPOX reactor units within the array as illustrated by the wavy arrows in FIG. 4C .
  • a single, or two, or at most a few, igniter(s) that avoid direct contact with CPOX reactor units provides several advantages over a CPOX igniter system in which each CPOX reactor unit has its own physically attached or integrated igniter. While use of the latter ignition system is contemplated by the present teachings, identification of an inoperative igniter can be problematic and its removal and replacement without damage to the CPOX reactor unit of which it is a part and/or disturbance to other reactor units in the array can be difficult. Accordingly, a single (or a few) igniter(s) appropriately positioned within an array or plurality of CPOX reactor units can permit easy and simple identification and extraction from CPOX reformer of a failed or defective igniter, and its replacement with an operative igniter.
  • each igniter to ignite a 2x7 array of CPOX reactor units it can be advantageous to reverse the positions of igniter 435 and thermocouple 440 on one side of chamber 436 relative to the positions of igniter 435 and thermocouple 440 on the other side of the chamber, particularly where there can be significant thermal communication between the two chambers.
  • Such an arrangement has been observed to result in a more rapid initiation of CPOX within the CPOX reaction zones of each separate array of CPOX reactor units.
  • a single igniter can be used to initiate CPOX within the CPOX reaction zones of the CPOX reactor units within the chamber.
  • Chamber 436 shown in FIGS. 4B , 4C and 4D can contain a pressurized fluid such as a pressurized gas that can act as a hydrogen barrier as discussed herein.
  • Chamber 436 can be an air-tight chamber.
  • chamber 436 is generally located to include in the chamber the CPOX reaction zone (e.g., the section of the gas permeable wall including a CPOX catalyst) of each of CPOX reactor units 408 as well as to include igniter 435 and thermocouple 440 .
  • the chamber includes some of the CPOX reaction zone, one or more walls of the chamber can act as a hydrogen barrier where the CPOX reactor units traverse or extend through the walls, for example, above and below the interior of the chamber as shown.
  • a pressurized fluid conduit such as a pressurized gas conduit (not shown) can provide operable fluid communication between the interior of the chamber and a source of pressurized or compressed fluid such as compressed air.
  • the pressurization of the chamber can be controlled using the appropriate valve and pressure sensor assemblies to provide sufficient fluid pressure for an adequate hydrogen barrier.
  • enlarged manifold portion 450 of manifold 426 of reformer 400 illustrated in FIGS. 4A and 4B includes upper housing structure 455, lower housing structure 456, manifold chamber 429, gaseous CPOX reaction mixture (gas) distributor 427 and gas distributor outlets 430 in fluid communication, for example, gaseous flow communication, with inlets 431 of tubular CPOX reactor units 408 .
  • Inlet ends 457 of tubular CPOX reactor units 408 are firmly seated within cavities 458 formed within upper housing structure 455 and are engaged in gas-tight relationship therewith by O-ring gaskets 459.
  • Gaseous CPOX reaction mixture flows through outlets 430 of gas distributor 427, through inlets 431 of tubular CPOX reactor units 408 and into CPOX reaction zones 409, where the gaseous CPOX reaction mixture undergoes gaseous phase CPOX conversion to a hydrogen-rich, carbon monoxide-containing effluent reformate exiting the reactor units at their outlet ends 460 through associated outlets 454.
  • gas permeable wall 451 of each tubular CPOX reactor unit 408 includes an inner surface 461, an outer surface 462, an open gaseous flow passageway 463 enclosed by gas-permeable wall 451, a portion of which constitutes CPOX reaction zone 409, and a catalytically effective amount of CPOX catalyst 464 supported within and/or comprising the structure of at least the section of gas-permeable wall 451 corresponding to second region 453 and CPOX reaction zone 409.
  • a hydrogen barrier 465 is attached to outer surface 462 of gas-permeable wall 451.
  • An open gaseous flow passageway can allow for the substantially unimpeded flow of gaseous CPOX reaction mixture and hydrogen-containing reformate therein, a structural feature of CPOX reactor units of the present teachings that contributes to the low back pressure which is characteristic of the operation of gaseous fuel CPOX reformers of the present teachings.
  • back pressures of not more than about 746.5 Pa (3 inches of water; 0.0075 bar), ,for example, not more than about 497.7 Pa (2 inches of water), or not more than about 2. 248.8 Pa (1 inch of water), , are readily achievable.
  • a hydrogen barrier is associated with, for example, attached to or adhered to, an outer or external surface of the gas-permeable wall for at least that portion of the length of the CPOX reactor unit corresponding to its CPOX reaction zone.
  • Materials capable of functioning as effective hydrogen barriers should be thermally stable at the high temperatures typical of CPOX reactions and should be sufficiently dense to prevent or deter permeation or diffusion of reformate gases, particularly hydrogen, therethrough.
  • a variety of ceramic materials (inclusive of glasses and glass-ceramics) and metals meeting these requirements are known and are therefore suitable for providing hydrogen barrier.
  • Specific materials for hydrogen barrier include, for example, aluminum, nickel, molybdenum, tin, chromium, alumina, recrystallized alumina, aluminides, alumino-silicates, titania, titanium carbide, titanium nitride, boron nitride, magnesium oxide, chromium oxide, zirconium phosphate, ceria, zirconia, mulite and the like, admixtures thereof and layered combinations thereof.
  • the hydrogen barrier can be applied to at least that portion of an outer surface of a CPOX reactor unit wall corresponding to the CPOX reaction zone as a pre-formed layer, foil, film or membrane.
  • the hydrogen barrier can be bonded to the wall with a refractory adhesive.
  • a hydrogen barrier can be formed on an outer surface by employing any suitable deposition method, for example, any of the conventional or otherwise known ceramic-coating and metal-coating techniques such as spray coating, powder coating, brush coating, dipping, casting, co-extrusion, metalizing, and the like, and any of their many variations.
  • a suitable range of thickness for a hydrogen barrier will depend primarily on the hydrogen permeability characteristics of the selected barrier material and the gas permeability characteristics of the wall enclosing the CPOX reaction zone, such thickness being determined by those skilled in the art.
  • the thickness of a hydrogen barrier can vary from about 2 microns to about 15 microns, for example, between about 5 microns to about 12 microns.
  • a hydrogen barrier can be a pressurized fluid such as a pressurized gas associated with the external surface of a gas-permeable wall of a CPOX reactor unit, for example, at least the CPOX catalyst-containing wall section.
  • a pressurized fluid exterior to a CPOX reactor unit can create a barrier to prevent the loss of hydrogen through the gas-permeable wall that forms the CPOX reactor unit.
  • Pressurized fluids typically are pressurized gases, such as inert gases (e.g., nitrogen) and/or air.
  • pressurized air as a hydrogen barrier has the additional advantage of oxygen diffusing from the exterior to the interior of the CPOX reactor unit, which diffused oxygen can adjust the O:C ratio of the gaseous CPOX reaction mixture about to and/or being reformed, particularly where such a hydrogen barrier is used and present around the CPOX reaction zone.
  • the CPOX reactor units can be located in an air-tight chamber but for their inlets and outlets thereby to permit pressurization of a fluid such as a gas in the environment exterior to the CPOX reactor units, which pressurized gas can create a hydrogen barrier associated with the external surfaces of the CPOX reactor units.
  • a fluid such as a gas in the environment exterior to the CPOX reactor units
  • pressurized gas can create a hydrogen barrier associated with the external surfaces of the CPOX reactor units.
  • hydrogen is not produced in a CPOX reactor unit until the CPOX reaction zone, only the CPOX reaction zones of the CPOX reactor units are enclosed in an air-tight chamber that is pressurized with a fluid such as air.
  • the beginning of the CPOX reaction zone to the outlet can be enclosed in an air-tight chamber to permit a pressurized gas to be used as a hydrogen barrier.
  • a chamber as described herein can encompass a portion of the CPOX reaction zone while another form of a hydrogen barrier can be present encompassing the remainder of the CPOX reaction zone.
  • a conduit in fluid communication with the interior of the chamber can be used to pressurize the chamber with a fluid.
  • a pressurized fluid or gas conduit can provide operable fluid communication between the interior of the (air-tight) chamber and a source of pressurized or compressed fluid, such as a container a compressed gas such as compressed air.
  • CPOX reactor unit 408 illustrated in FIGS.
  • the number of such CPOX reactor units, their length, their internal and external diameters (defining the thickness of their gas-permeable walls) and the location, length and thickness of hydrogen barriers attached to outer surfaces of the gas-permeable walls will be determined by, among other things, the hydrogen-producing capacity of the CPOX reformer, which in turn is a function of several factors including the type, amount (loading and distribution of CPOX catalyst within the gas-permeable walls), the characteristics of the porous structure of walls, characteristics influencing the gas-permeability of the walls, (and therefore affecting the CPOX reaction) such as pore volume (a function of pore size), the principal type of pore (mostly open, i.e., reticulated, or mostly closed, i.e., non-reticulated), and pore shape (spherical or irregular), the volumetric flow rates of CPOX reaction mixture, CPOX temperature, back pressure, and the like.
  • the hydrogen-producing capacity of the CPOX reformer which in turn is a function of several factors
  • the desired mechanical performance characteristics of a particular gaseous fuel CPOX reformer will depend to a considerable extent on such factors as the thermal and mechanical properties of the material used for construction of the CPOX reactor units, the volume and morphology of the pores of the gas-permeable structure of the walls of the CPOX reactor units, the dimensions of the reactor units, particularly wall thickness, and related factors.
  • the gas permeability property of the catalytically-active wall structure of a tubular CPOX reactor unit enclosing a gaseous phase CPOX reaction zone should be such as to allow gaseous reformable fuel to enter freely and diffuse through such wall structure thereby making effective contact not only with surface CPOX catalyst but interior CPOX catalyst as well, if present.
  • CPOX reactor unit wall structures having limited gas permeability for the vaporized reformable fuel can be mass transport limited so as to impede significantly CPOX conversion of the gaseous reformable fuel to hydrogen-rich reformate.
  • catalytically-active reactor wall structures of suitable gas permeability promote CPOX conversion of the gaseous reformable fuel and selectivity for hydrogen-rich reformates of desirable composition.
  • CPOX reactor units having catalytically-active wall structures exhibiting optimal gas permeability properties for a particular gaseous reformable fuel to be processed.
  • Materials from which the catalytically-active wall structure of a CPOX reaction zone of a tubular CPOX reactor unit can be fabricated are those that enable such wall structures to remain stable under the high temperatures and oxidative environments characteristic of CPOX reactions.
  • Conventional and otherwise known refractory metals, refractory ceramics, and combinations thereof can be used for the construction of the catalytically-active wall structure of a CPOX reaction zone.
  • Some of these materials, for example, perovskites also can possess catalytic activity for partial oxidation and therefore can be useful not only for the fabrication of the catalytically-active wall structure of a CPOX reaction zone but also can supply part or even all of the CPOX catalyst for such structure.
  • At least the section of the wall of a CPOX reaction zone or including a CPOX catalyst of a CPOX reactor unit can be made of or can include a perovskite.
  • a perovskite For example, greater than about 20%, greater than about 30%, greater than about 40%, greater than about 50%, greater than about 60%, greater than about 70%, greater than about 80%, or greater than about 90% by weight of such wall section can be perovskite.
  • Such a wall section can be made entirely of a perovskite, or the entire wall of a CPOX reactor unit can be made of a perovskite or can include the percentages of a perovskite described herein.
  • the balance of the materials of the section of the wall at least corresponding to the CPOX reaction zone can include at least one component selected from metals, ceramics, refractory binders, and CPOX catalysts other than a perovskite.
  • the perovskite can be at least one member selected from LaNiOs, LaCoO 3 , LaCrO 3 , LaFeO 3 and LaMnO 3 .
  • Perovskites can include lanthanum strontium manganite, lanthanum strontium ferrite, lanthanum strontium cobalt ferrite, lanthanum calcium manganite, lanthanum strontium chromite, lanthanum strontium gallate magnesite, and combinations thereof.
  • the perovskite When present as a catalyst, the perovskite can be La 1-x Ce x Fe 2 O 3 , LaCr 1-y RuyO 3 , La 1-x Sr x Al 1 - y Ru y O 3 and La 1-x Sr x Fe 2 O 3 , including combinations thereof, where x and y are numbers ranging from 0.01 to 0.5.
  • other appropriately transition metal-doped perovskites can be used in the practice of the present teachings.
  • Refractory metals include titanium, vanadium, chromium, zirconium, molybdenum, rhodium, tungsten, nickel, iron and the like, their combinations with each other and/or with other metals and/or metal alloys, and the like.
  • Refractory ceramics are a class of materials for the construction of the catalytically-active wall structures due to their relatively low cost compared to many refractory metals and metal alloys that are also useful for this purpose.
  • Suitable refractory ceramics for the construction of a CPOX reaction zone include, for example, perovskites, spinels, magnesia, ceria, stabilized ceria, silica, titania, zirconia, stabilized zirconia such as alumina-stabilized zirconia, calcia-stabilized zirconia, ceria-stabilized zirconia, magnesia-stabilized zirconia, lanthana-stabilized zirconia and yttria-stabilized zirconia, zirconia stabilized alumina, pyrochlores, brownmillerites, zirconium phosphate, silicon carbide, yttrium aluminum garnet, alumina, alpha-alumina, gamma-alumina, beta-alumina, aluminum silicate, cordierite, MgAl 2 O 4 , and the like, various ones of which are disclosed in U.
  • the total or overall fuel conversion capacity of a CPOX reformer of a given design will be the sum of the fuel conversion capabilities of its individual CPOX reactor units.
  • the minimum distance between adjacent CPOX reactor units will be such that in the steady-state mode of operation of the reformer, the temperature of the reactor units does not exceed a predetermined, or preset, maximum, and the maximum distance between adjacent CPOX reactor units is that distance beyond which the CPOX reaction fails to be initiated within one or more reactor units during a start-up mode of operation of the gaseous fuel CPOX reformer or the temperature within one or more CPOX reactor units falls below a predetermined, or preset, minimum intended for the steady-state mode of operation of the reformer.
  • the minimum and maximum distances between adjacent CPOX reactor units readily can be determined for a given reformer section design employing routine testing methods.
  • CPOX catalysts including catalyst systems
  • methods of incorporating catalyst within a porous substrate or support specifically, a gas-permeable wall of the a CPOX reactor unit, and patterns of catalyst distribution including, but not limited to, catalyst confined to a particular section of a wall, catalyst loading increased along the length of a reactor unit and/or decreased from an inner surface of a wall to its outer surface, CPOX catalyst that varies in composition along the length of the reactor unit, and similar variants.
  • catalyst loading within a wall of a CPOX reactor unit from the start of a CPOX reaction zone to, or near, the end thereof can be helpful in maintaining a constant CPOX reaction temperature with this zone.
  • CPOX catalysts that can be utilized herein are the metals, metal alloys, metal oxides, mixed metal oxides, perovskites, pyrochlores, their mixtures and combinations, including various ones of which are disclosed, for example, in U.S. Patent Nos. 5,149,156 ; 5,447,705 ; 6,379,586 ; 6,402,989 ; 6,458,334 ; 6,488,907 ; 6,702,960 ; 6,726,853 ; 6,878,667 ; 7,070,752 ; 7,090,826 ; 7,328,691 ; 7,585,810 ; 7,888,278 ; 8,062,800 ; and, 8,241,600 .
  • CPOX catalysts While numerous highly active noble metal-containing CPOX catalysts are known and as such can be useful herein, they are generally less used than other known types of CPOX catalysts due to their high cost, their tendency to sinter at high temperatures and consequently undergo a reduction in catalytic activity, and their proneness to poisoning by sulfur.
  • Perovskite catalysts are a class of CPOX catalyst useful in the present teachings as they are also suitable for the construction of the catalytically-active wall structures of a CPOX reactor unit.
  • Perovskite catalysts are characterized by the structure ABX 3 where "A" and “B” are cations of very different sizes and "X” is an anion, generally oxygen, that bonds to both cations.
  • suitable perovskite CPOX catalysts include LaNiO 3 , LaCoO 3 , LaCrO 3 , LaFeO 3 and LaMnO 3 .
  • A-site modification of the perovskites generally affects their thermal stability while B-site modification generally affects their catalytic activity.
  • Perovskites can be tailor-modified for particular CPOX reaction conditions by doping at their A and/or B sites. Doping results in the atomic level dispersion of the active dopant within the perovskite lattice thereby inhibiting degradations in their catalytic performance. Perovskites also can exhibit excellent tolerance to sulfur at high temperatures characteristic of CPOX reforming.
  • doped perovskites useful as CPOX catalysts include La 1-x Ce x FeO 3 , LaCr 1-y Ru y O 3 , La 1-x Sr x Al 1-y Ru y O 3 and La 1-x Sr x FeO 3 wherein x and y are numbers from 0.05 to 0.5, for example, from 0.05 to 0.2, depending on the solubility limit and cost of the dopants.
  • a CPOX reactor unit can include a first, upstream region that is substantially devoid of CPOX catalyst and can extend from its inlet end to a second, downstream region that contains a CPOX catalyst.
  • the second, downstream region typically extends from the end of the first region to its reformate effluent outlet, although the amount of catalyst near the outlet can decline.
  • the length of these regions relative to the entire length of the CPOX reactor unit can vary considerably.
  • a first region can extend from about 20% to about 60%, for example, from about 30% to about 40% or about 50%, of the length of a CPOX reactor unit, with a second region extending the remainder of the length of the CPOX reactor unit.
  • first region 452 remains at a considerably lower temperature than second region 453 (corresponding to CPOX reaction zone 409) allowing manifold housing 428 of manifold 426 of FIG. 4A to be fabricated from any of numerous kinds of low cost, readily moldable thermoplastic or thermoset resins.
  • CPOX reactor unit 408 in addition to the circular cross section shown in FIG. 4G , can assume other cross sectional configurations such as those illustrated in FIGS. 4H and 41.
  • FIG. 4H illustrates a CPOX reactor unit having an alternating concave-convex, or bilobate, cross section.
  • CPOX reactor units having such a cross sectional configuration can be especially advantageous where their outlet sections are to be joined to, or mated with, similarly configured tubular solid oxide fuel cell (SOFC) units as in the SOFC fuel cell assembly of co-pending, commonly assigned U.S. Patent Application Publication No. 2013/0230787, by Finnerty et al. .
  • SOFC solid oxide fuel cell
  • the outlets of two or more CPOX reactor units of a multi-tubular CPOX reformer can be in fluid communication with each other (and with additional outlets of CPOX reactor units) and the hydrogen-rich reformate from the outlets can be combined prior to introduction into a fuel cell.
  • the hydrogen-rich reformate effluent from two or more CPOX reactor units can be combined in a manifold or similar device and/or one or more conduits and then introduced into a fuel cell, which could be a multi-tubular fuel cell or a single fuel cell unit.
  • a CPOX reformer of the present teachings can be adapted to various applications depending on its end use, for example, providing hydrogen-rich reformate to a single or multi-tubular fuel cell unit.
  • Centrifugal blower system 402 of gaseous CPOX reformer 400 shown in greater detail in FIGS. 4J and 4K , disclosed in co-pending, commonly assigned U.S. Patent Application Publication No. 2012/0328969, by DeWald et al. .
  • a centrifugal blower system can possess the ability to make rapid adjustments in the volume of air introduced into a conduit and/or in the rate of flow of the gaseous fuel-air mixture to CPOX reactor units in response to changes in the demand for product hydrogen-rich reformate that single centrifugal blowers of comparable air flow capacity are incapable of providing, as explained herein, without resorting to blowers of relatively high power consumption.
  • Single centrifugal blowers such as those utilized to provide gas flows for the operation of known and conventional reformers require suitable control of the full range of motor revolutions per minute (rpm) in order to meet fluctuating gas flow demands.
  • rpm revolutions per minute
  • optimum performance of a single blower for meeting these requirement can involve employing a blower having an impeller of relatively small size driven at relatively high rpm, for example, about 20,000 rpm and above, or a blower having an impeller of relatively large size driven at relatively low rpm, for example, below about 20,000 rpm and more commonly, below about 10,000 rpm.
  • the first arrangement i.e., a single blower having a relatively small impeller driven at relatively high rpm
  • the second arrangement i.e., a single blower having a relatively large impeller driven at relatively low rpm, can make control and fine tuning of the blower output more difficult due to the greater inertia of a large impeller.
  • a single blower having a relatively high inertia impeller must be overdamped when tuning the blower for its expected range of gas pressure and flow capacity.
  • the effect of this overdamping to compensate for the relatively high inertia of the impeller is to cause the blower to be slow in responding to changing, and often rapidly changing, gas flow requirements.
  • This characteristically slow response of a single centrifugal blower having a relatively high inertia impeller can require a more complicated control system for satisfactorily responding to fluctuations in gas flow demand.
  • Utilizing a centrifugal blower system to drive gas flows within a CPOX reformer can enable the system to benefit from both low inertia impellers for control as well as low drive motor rpm and power draw to meet quickly target gas flow and pressure requirements.
  • Controlling one or more blower units in an interconnected series of blowers such as a centrifugal blower system to provide a major portion of the target gas pressure and gas flow, for example, about 60% to about 90% of the target gas pressure and gas flow, can enable the remainder of the target gas pressure and gas flow to be provided by one or more other blower units in the system.
  • centrifugal blower system 402 includes first centrifugal blower unit 486 connected to second centrifugal blower unit 487 through duct 488.
  • First blower unit 486 includes casing 489 having axial inlet 490 and radial outlet 491, impeller 492 disposed within casing 489 for drawing ambient air at a first pressure into axial inlet 490 and expelling air at a second higher pressure through radial outlet 491, and electric motor 493 for driving impeller 492.
  • Second blower unit 487 includes casing 494 and, as shown by the cutaway section of duct 488 in FIG.
  • Second blower unit 487 further includes radial outlet 498 and outlet gas stream housing 499, the discharge end 484 of which can be connected to one end of a conduit, for example, conduit 404 of gaseous fuel CPOX reformer 400 of FIG. 4A , as indicated by the dotted lines.
  • FIGS. 4J and 4K indicate the general direction of the ambient air through the radial outlet of each blower unit in the series of blowers constituting centrifugal blower system 402 .
  • the trajectory of the ambient air stream expelled through outlet 491 of first blower unit 486 and the trajectory of the ambient air stream expelled through outlet 498 of second blower unit 487 are not parallel to their respective outlets but are at some angle thereto.
  • Turbulence can be advantageously minimized or avoided so as to reduce or eliminate it as a source of back pressure in a centrifugal blower system.
  • it can be advantageous to arrange the angle of gas stream housing 499 so that its interior walls will be approximately parallel to the trajectory of the ambient air discharged through outlet 498 of second blower unit 487.
  • the optimum geometry of the interior walls of a duct relative to the trajectory of its gas stream and the angle of offset of a gas stream housing can be readily determined for a given centrifugal blower system employing routine experimentation.
  • interior, or guiding, surfaces of duct 488 and interior, or guiding, surfaces of gas stream housing 499 can be pitched at an angle ⁇ of from about 12° to about 20°, for example, from about 14° to about 18°, relative to outlets 491 and 498.
  • FIG. 5 presents graphical data demonstrating the relationship between the oxygen (O) to carbon (C) molar ratio of propane-air CPOX reaction mixtures and CPOX reaction temperature.
  • O oxygen
  • C carbon
  • gaseous CPOX reaction mixtures having higher O to C molar ratios can be utilized during the start-up mode of operation of the reformer.
  • the higher operating temperatures associated with fuel-lean CPOX reaction mixtures can facilitate a more rapid increase in CPOX catalyst temperature and reduced time to steady-state operation.
  • a fuel-lean ratio tends to help inhibit coke formation before the CPOX catalyst has attained its optimum temperature and become fully activated.
  • Reducing the O to C molar ratio lowers the catalyst temperature and can enable more fuel to be processed without losing thermal control of the CPOX reactor units and in turn, the fuel vaporizer unit.
  • the opposite action can be taken for the shut-down operation, i.e., fuel flow is reduced at a maintained O to C molar ratio.
  • the O to C molar ratio can be increased to prevent or minimize coking as the CPOX catalyst deactivates.
  • the CPOX reformer can be shut down when the temperature of the CPOX reaction mixture falls below about 500 °C.
  • the flow of oxygen-containing gas can be continued for up to about 15 to 20 seconds or so after fuel flow has been discontinued.
  • a shut-down procedure can allow for removal of fuel from the reformer that can be contained within a conduit or a section of fuel line between a fuel control valve and locus of introduction of the fuel into the conduit.
  • This control characteristic can be influenced by various reformer components including the particular delivery system and controller unit components utilized in a specific reformer design.
  • the O to C molar ratio of the fuel-air CPOX reaction mixture can be controlled during the operation to tailor its output thermal conditions, with the understanding that changing the O to C molar ratio can result in changes to the quality and/or composition of the reformate.
  • Different CPOX catalysts can affect the operational windows and CPOX temperatures.
  • different fuels gaseous or liquid

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